Breadstuff flavoring compositions and methods of making them



United States Patent 3,304,184 BREADSTUFF FLAVORING COMPOSITIONS ANDMETHODS OF MAKING THEM Lazare Wiseblatt, Chicago, 11]., assignor toResearch Corporation, New York, N.Y., a corporation of New York NoDrawing. Original application Oct. 10, 1962, Ser. No. 229,748, nowPatent No. 3,268,555, dated Aug. 23, 1966. Divided and this applicationJune 7, 1966, Ser. N 0. 535,628

8 Claims. (Cl. 99-90) This application is a divisional application of myapplication Serial No. 229,748, filed October 10, 1962, now Patent No.3,268,555.

This invention relates to novel flavoring compositions for use infoodstuffs and the like and to methods of making them.

I have found that a group of new and useful flavoring compositions maybe made by reacting aliphatic ketols with amino acids or with certaindecarboxylation products thereof such as pyrrolidine.

As one component of the reaction mixture any of the naturally occuringa-amino acids may be used, either in the racemic or in one of theoptically active forms. Among the aliphatic ketols which may be used toproduce useful compositions by the method of the invention are1,3-dihydroxyacetone, l-hydroxy-Z-propanone, glyceraldehyde and theirlower alkyl homologs and lower alkanoic esters such asacetylmethylcarbinol and the acetic acid ether of l-hydroxy-Z-propanone,respectively.

In general, the character of the flavoring composition obtained isaffected more by the amino acid used than by the ketol. Most of thedifferent amino acids produce compositions of typically differentcharacter and strength but most of the compositions have a pleasingaroma except those obtained from sulfur containing acids such ascysteine. Pyrrolidine gives a flavoring composition having a distinctcracker-like aroma like that obtained with its carboxylic acidderivative proline.

The reaction may be carried out in aqueous solution or in water-miscibleor water-immiscible solvents such as ethyl alcohol, pyridine andtoluene. Preferably the reaction is carried out in aqueous solution at apH in the range from about 4 to about 8.5

The following examples are illustrative of the principles of theinvention:

Cracker flavor (A) From proline.An aqueous solution containingapproximately equirnolar amounts of L-proline and 1,3- dihydroxy-acetonedevelops a brown color and distinctly crackerlike aroma on boiling for afew minutes. Prolonged boiling achieves only a moderate intensificationof the aroma, while the solution becomes extremely dark. The aromaintensity achieved shows relatively little pH dependence within the pHrange 4.0-8.5. Under more acidic conditions, the aroma synthesis andbrowning are both drastically inhibited, while under more basicconditions there arise objectionable odors, and browning becomes severe.Phosphate ions and potassium bromate both exhibit catalytic propertiestowards aroma production; the former, however, also catalyzes browning,while the latter must be limited to low concentrations if the reactionmixture is to be incorporated in bread doughs.

Proline and 1,3-dihydroxy-acetone react very satisfactorily innon-aqueous media to yield the cracker aroma. Ethyl alcohol, pyridine,and toluene are satisfactory solvents. In every instance,decarboxylation of the proline is evidenced by the vigorous evolution ofcarbon dioxide and a progressive development of basicity in the reactionmixture. When toluene is used, there is azeotropic distillation of waterwith the solvent, suggesting the splittingout of water in a condensationreaction.

3,304,184 Patented Feb. 14, 1967 (B) From pyrrolidine.-One-half mole(35.6 grams) of ice-cold pyrrolidine is added dropwise to /2 mole (30grams) of glacial acetic acid, with cooling in an ice bath. When all thepyrrolidine has been added, the resulting golden-yellow syrup is warmedgently on a water-bath, and /2 mole (45 grams) of 1,3-dihydroxy-acetoneis added in small portions. The condensation reaction is exothermic, andwarming must be limited to prevent violent frothing.

After all the 1,3-dihydroxy-acetone has gone into solu tion, thereaction mixture is an opaque, viscous, dark brown liquid. This isdistilled at atmospheric pressure; distillate begins to come over at 102C., and when the vapor temperature attains 0., there is a temporarycessation of distillation. The distillate boiling between 102110 C.,about 20 ml. in volume, contains most of the desired aroma compound,together with acetic acid and water. To isolate the aroma compound, thedisti1 late is neutralized with sodium bicarbonate, saturated with salt,and the product extracted into chloroform. The extract is dried overanhydrous sodium sulfate and evaporated under vacuum to remove thesolvent. The yield is about 3 grams.

The following table lists the aromas of the flavoring compositionsproduced by boiling aqueous mixtures of 1,3-dihydroxy-acetone with otheramino acids:

Amino acid: Description of aroma Lysine Strong, like dark corn syrup.Valine Strong, yeasty, protein hydrolysate. Alanine Weak, caramel.

Glutamic acid Moderate, chicken broth. Aspartic acid Very weak.

Arginine Very weak. Hydroxyproline Weak, vaguely like proline.Phenylalanine Very strong, hyacinth.

Leucine Strong, cheesy, baked potato. Isoleucine Moderate, crust.

Serine Weak, vaguely breadlike. Threonine Very weak.

Methionine Baked potato.

Glycine Baked potato.

Histidine Very weak.

Tryptophan Strong, indole.

Tyrosine Very weak.

Modified flavors may be made by using various mixtures of amino acids insuitable proportions.

The method of the invention may be utilized either by adding theappropriate reactants to the food batch prior to baking or cooking, sothat the baking or cooking provides the heat required for flavorgeneration, or by preforming the flavoring compositions in a suitableliquid re action medium which may be blended into the food batch eitheras such or after concentratiomof the flavor substances.

For example, when an aqueous solution of proline and1,3-dihydroxy-acetone was boiled for 15 minutes and added to achemically-leavened instant bread mix developed by the QuartermasterFood and Container Institute for the Armed Forces at a level equivalentto 0.0375 proline and 0.03% 1,3-dihydroxy-acetone (based on flourweight), the bread with this addition was ranked best in flavor of anyof the levels tested and far superior to the control. The flavorimprovement was even more notable when toast was made from these breads.

A further improvement resulted when the proline-1,3- dihydroxy-acetonepreboiled mixture was added together with 0.005% each of isoleucine,valine and alanine, and 0.0013% of 1,3-dihydroxy-acetone; the freshbread had an aroma which seemed deficient only in the alcoholiccharacter of normally flavorful yeast-leavened bread.

Thus a formulation based on 100 pounds of flour would be prepared asfollows:

17 grams of L-proline 13.6 grams of 1,3-dihydroxy-acetone 500 ml. ofwater (Boil together for 15-20 minutes) To the cooled solution add 2.25grams each of alanine, valine and isoleucine, and 5.9 grams of1,3-dihydroxyacetone. Adjust the volume, if necessary, to 500 ml., or toone pint (whichever is most convenient), This mixture replaces an equalvolume of Water in the dough.

I claim:

1. A method of imparting flavor to breadstufls which comprisesincorporating in the breadstuff a compound selected from the groupconsisting of pyrrolidine and proline and an aliphatic ketol selectedfrom the group consisting of 1,3-dihydrxyacetone, glyceraldehyde,acetylmethylcarbinol, l-hydroxy-Z-propanone and l-hydroxy-Z- propanoneacetate and thereafter heating the breadstutf.

2. A method of imparting flavor to breadstutfs which comprisesincorporating in the breadstufis proline and an aliphatic ketol selectedfrom the group consisting of 1,3- dihydroxyacetone, glyceraldehyde,acetylmethylcarbinol, l-hydroxy-Z-propanone and l-hydroxy-Z-propanoneacetate and thereafter heating the breadstuff.

3. A method of imparting flavor to breadstufis which comprisesincorporating in the breadstuif proline and 1,3- dihydroxyacetone andthereafter heating the breadstuif.

4. A method of imparting flavor to breadstuffs which comprisesincorporating in the breadstuff a flavoring composition obtained byheating a compound selected from the group consisting of pyrrolidine andproline with an aliphatic ketol selected from the group consisting of1,3- dihydroxyacetone, glyceraldehyde, acetylmethylcarbinol,1-hydroXy-2-propanone and l-hydroxy-Z-propanone acetate.

5. A method of imparting flavor to breadstuffs which comprisesincorporating in the breadstufl a flavoring composition obtained byheating proline with an aliphatic ketol selected from the groupconsisting of 1,3-dihydr0xyacetone, glyceraldehyde,acetylrnethylcarbinol, l-hydroxy- 2-propanone and l-hydroxy-Z-propanoneacetate.

6. A method of imparting flavor to breadstufls which comprisesincorporating in the breadstuif a flavoring composition obtained byheating pyrrolidine with an aliphatic ketol selected from the groupconsisting of 1,3-dihydroxyacetone, glyceraldehyde,acetylmethylcarbinol, l-hydroxy- 2-propanone and l-hydroxy-Z-propanoneacetate.

7. A method of imparting flavor to breadstuifs which comprisesincorporating in the breadstuff a flavoring composition obtained byheating proline with 1,3-dihydroxyacetone.

8. A method of imparting flavor to breadstutfs which comprisesincorporating in the breadstuff a flavoring composition obtained byheating pyrrolidine with 1,3-dihydroxyacetone.

References Cited by the Examiner UNITED STATES PATENTS 3,220,850 11/1965Kirk 9990 A. LOUIS MONACELL, Primary Examiner.

H. H. KLARE, Assistant Examiner.

1. A METHOD OF IMPARTING FLAVOR TO BREADSTUFF WHICH COMPRISESINCORPORATING IN THE BREADSTUFF A COMPOUND SELECTED FROM THE GROUPCONSISTING OF PYRROLIDINE AND PROLINE AND AN ALIPHATIC KETOL SELECTEDFROM THE GROUP CONSISTING OF 1,3-DIHYDROXYACETONE, GLYCERALDEHYDE,ACETYLMETHYLCARBINOL, 1-HYDROXY-2-PROPANONE AND 1-HYDROXY-2PROPANONEACETATE AND THEREAFTER HEATING THE BREADSTUFF.